Resinification of oxidized terpene hydrocarbons



Patented at. 21, 1939 UNITED STATES PATENT OFFICE- nEsmmrcA'rroN or oxrmzun 'rcnrnnn nrnaocmous Joseph Hidy James, Pittsburgh, Pa., assignor to Clarence P. Byrnes,

Sewickley', Pa., trustee No Drawing. Application October 1. 1935, S0118!" N0. 43,082

1 Claim.

In variouspatents and pending applications, I have described my vapor or gaseous phase partial oxidation process, preferably in the presence of a catalyst, for making partial oxidationproducts from aliphatic hydrocarbons whether saturated or unsaturated, as well as from hydrocarbons containingcyclated bodies of naphthenic type; see for example, my re-issue Patent No.

18,522 dated July 12, 1932, and other of my,

patents, and copending' applications Ser. No. 272,567 iiled January 22,- .1919, Patent No.

2,085,221; Ser. No. 435,355 filed January 6, 1921,

Patent No. 2,054,571, and Ser. No. 310,437, filed October 4, 1928.

v The partial oxidation product so produced contains groups of oxidized bodies in the range from alcohols to organic acids, each group or class containing similar bodies of different molecular weights. For example, there are alcoholic groups, ketonic groups, aldehydic groups, acidic groups, etc. I have found that excellent resins may be produced by combining the partially oxidized products or portions thereof with polyhydric alcohols, such as glycerol or glycol; and I have also found that even where the acid content is not of a dibasic type, but of an oxygenated type, the reaction with such polyhydric alcohols occurs. This, therefore, opens up a field for a large number of resin compounds which may be cheaply prepared, and especially from the liquid products produced by applying my vapor phase catalytic oxidation process to aliphatic or naphthenic hydrocarbons,

and to terpenic hydrocarbons such as pine oil.

.I have' further discovered that my process is peculiarly adapted to the partial oxidation of terpenic hydrocarbons whichare specially adapted therefor. The structure of such terpenic hydrocarbons is a ring type body having, however, a double bond so located that in my process the terpenes act morelike aliphatic compounds than like aromatics.

that the structurefis peculiarly open to oxygen attack by my vapor phase process. Consequently the process may be carried out at relatively lower temperatures than when applied to straight aliphatic hydrocarbons for example, at 200 C. or lower. Furthermore, the product thereof is pecularily adapted for certain purposes such as resins. The process may be applied to all. vaporizableterpenesand especially to the turpentine and pine oil products of the Southern- Pine Naval Stores Industry. Taking pine oil 55 as an example from the Georgia plant of one This double bond is so located CHs-C- CHs This cyclic structure has more of the aliphatic than of the aromatic characteristics and 1 its double bond acts like an olefin, in my vapor phase process of oxidation.

The double bond in alpha pinene offers a point .of oxygen attack, the result being the opening of the chain and, on a less degreeof oxidation,- forming a carboxyl group on one carbon atom at the rupture and a ketone group onthe other. Still more vigorous oxidation would break the bond between the central carbon atom and the. ring carbbn to which it is attached, likewise introducing a hydroxyl vketon ic group at the other. The process may be applied to other companies, this showed terpene hydrocarbons, producing intermediate oxidation products of the alcoholic, acidic, ketonic and aldehydic types. The resulting oxidation mixtures may either be subjected -to methods of group separation or may be used in toto.

Ezample Taking ,Georgia pine oil of a specific gravity (by volume) passing over at 209 C. and an end point of 226 'C.

The partial oxidation apparatus was of my triple-screen type, with molybdenum. oxides as the catalyst, this being of the type whichwas-nonvolatile at the temperatures used. In such case at =.936, Engler distillation; initial C.

,air was added in front of the first screen and between the first and second screen and again between the second and third screen. The rate of feed into thevaporizer was 8 liters per hour and.

the air rates 62 liters of air per hour at the first screen; 50' liters of air per hour at the second screen, and 50'liters of" air per hour at the third screen. The temperatures were maintained be- -lation at 90. C. 50% (by volume). passing over at 196 C. Decomposition of the residual liquid acids.

inthe distilling fiask started at about the 90% point where the temperature was236 C. 80- dium hydroxide saponification removed by volume from the total oxidation mixture. showing the presence of a large amount of carboxylic The sulphuric-acid test gave-a contrac-- tion of 64% by volume, while the sodium acid sulphite test for aldehydes and methyl ketones showed 10%.

Further proof that the greater part of the oil fed had been converted into partial oxidation products was shown by the fact that the total? product di solved nitrocellulose without an concentration of said oxidized product.

The partial oxidation product thus obtained may be used for several purposes. Among these would be the preparation of cellulose solvents and plasticizers; solvents for synthetic resins; using the oxidized product as raw material for the production of synthetic resins, either by polymerizing the product'itself, or by combining it or products thereof with phenols or with polyhydric alcohols, or with combinations of them. v

Changes may be'made-in the'terpenic hydrocarbon used as raw material; one or more catalytic layers or screens may be .used; a gaseous catalyst may be. used or no catalyst at all; pure oxygen may be used instead-of air; the process may be carried :out at subatmospheric', atmospheric or superatmospheric pressures; partial oxidation products may be recovered by condenserscrubber systems after each reaction and .before the-exit stream passes to another reaction-chamber: in the plural-screen type :1- and other'changes may be made in this step,

One of the important products obtained from such partial oxidation product or terpenes is the production of resins. I will now give examples of the production of resins from. my partial oxidation products,'and particularly as to three groups of re ins, the first group being formed by the reaction between my ,partial oxidation products of aliphatic or terpenic hydrocarbons and .polyhydric alcoholssuch as glycerol; the second group relating to the formation of resins by the reaction of the terp'enic partial oxidation products-with phenols and thethird groupto resins formed by adding the oxygenated acids to certain carbohydrates preferably inthe presence of a catalyst. r 7 First group: In this group, the oxygenated acids formed by -my vapor phase catalytic air oxfidation of Pennsylvania gas oil' were combined :with' glycerol to form resins. k

Example Is -5' grams of oxygenated acids exctracted from an oxidation mixture were heated with 20 cc. glyceroL'using 2 cc. of concentrated shed at 210 and didnot melt up to 250 C.

C. in the course of an hour, and the heating continued at this temperature for about four hours. The liquid mass (liguid from excess of glycerol) was poured into 300 cc. of hot water todissolve the unreacted glycerol. The washing was repeated until all the free glycerol was removed. The resin thus produced was of a brown color, showed darkening at C. and on a meltmg point determination, it showed no fusion up 'to 240 C. It was insolublein benzol, but dis-.

solved in a solvent prepared from the vapor phase catalytic oxidation of naphthenic gasoline, such solvent containing alcohols, aldehydes, ketones and esters (1 part-resin to 5 parts of solvent). On evaporation an excellent fllm which was hard and tough resulted. A

Example 2.-5 grams of the oxidized product including oxygenated acids was combined with 2 cc. of denatured alcohol to aid in initial solution and reaction. A mixture was then made of this with 20 cc. of glyoerine, using as a catalyzer one gram of anhydrous aluminum chloride. .The mixture was gradually warmed up to 100 C. dur-. ing one hour and heating continued at that temperature for about four and one-half hours. The

. treatment with water and washing to remove excess water and glycerol was the same as in Experiment 1. A re in was obtained which dark- It was not soluble in benzol or amyl alcohol. It dissolved (1 part to 20 parts) inthe oxidized gasoline solvent above referred to and formed a very hard and tough film on evaporation.

vExample 3.-Here I used a mixture of dibasic acid produced by a secondary. oxidation of the partial oxidation product obtained by vapor phase oxidation of Pennsylvania spindle oil, nitric acid being used for thisfurther oxidation. 5 grams 40 of the dibasic acid thus obtained was combined with 20 cc. of denatured alcohol to dissolve the acids and then mixed with 20 cc.' of glycerol and one gram'of anhydrous aluminum chloride as a catalyst. The mixture was heated gently. for 20 45 minutes to start the reaction and to evaporate the alcohol. The heating was-continued at 110 C. forv five hours. The remainder of the process was the same as in Example v1. Light brown resin was obtained with a melting point 50 .of about 48 C. This resin was readily soluble in benzol'and on evaporation left a tough film, but not having the hardness of the film left by the evaporation of the oxidized gasoline solvent.

- Example 4.4 cc. of oxidized pine oil was ll mixed with -5-cc; of glycerine, usingl gram of anhydrous aluminum chlorideasa catalyst: The mixture was gradually heated up'to C. during three hours, and the heating continued at about that temperature for about three hours longer. A- brown' resin resulted which separated from the glycerine which had not. entered the reaction. A melting point determination of theresin showed an initial softening at 84 C. and

complete liquefaction at 95 C. In the solvent 6| test, it wasfound easily soluble in benzol, forming a hard and' brittle film on evaporation. It was also easily solublein the oxidized gasoline "above referred to, leaving a hard and tough film hour and heated at that temperature four hours longer. A hard brown resin resulted.

A solvent test showed it was readily soluble in bensol, leaving on evaporation'a non-uniform oline'above referred to, this. resin dissolved readily, leaving atough film ,which'was somewhattach. The melting point determination vof this resin showed initial softeningat C. and com-,,

plete liquefying at 120' C.

' Second group: In this group, resins we'repre pared by reacting on oxidized pine oiiproduced -by catalytic vapor phaseoxidation of terpene hydrocarbon with phenol, using different catalysts. tion products condense of themselves to form resins, as shown. in Example 5, and also readily condense with phenols-making resins ofremark able quality. v

l'mmple 6.'5 cc. of oxidized pine oll was mixed with cc. of phenol, using 1 gram of anhydrous aluminum chloride as a catalyst. This was heated to 180 C. for ten minutes, and then at 150 C. for five hours. A dark brown resin resulted which, on melting point determination, showed'initial softening at 62 C. andcomplete liquefaction at C.- The resin dissolved readily in benzol, leaving a tough hard film. It dissolved even more readily in the oxidized gasoline above referred to and left' on evaporation agasoline which was very hard and tough.

Example 7.A mixture was made of-5 cc. of

V pine oil; 5 cc. of phenol and 1 cc. of caustic soda solution. This was heated for two hours at 150 0.3116 produced aresin which was solid at roomtemperature. It was a light brown color and softened at 89.5" C. and became completely liquid at 114 C. I It dissolved withsome difiiculty 'in' benzol, leaving a hard tough film. It was i readily soluble in the oxidized oil solvent giving a very hard tough film on determination.

.lrample. 8.5 cc.- of oxidized pine oil was mixed with 5 cc. of phenol and 1 cc. of aniline. After'two hours heating at 150 0., the resin was solid 'at room temperature. It gave a sharp melting point at 70 C. and the resin was brown in color. In benzol it dissolved readily giving an excellent film-hard and tough. It dissolved easily in the oxidized gasoline solvent, giving. an excellent film both as to hardness and toughgroansfor about.

poor characteristics. In the. oxidized gas- I have found that these terpene oxidewas then warmed to bination with phenols,

. especially by continued In the wimp. resins are prepared by asaing the oxygenated acids separated from my pal'- with one-half gram of anhydrous aluminum added as a catalyzer. The solution was allowed to stand for-24' hours at room temperature and 50 C. and held ere for 12 hours. A resin separated out andthe alcohol was finallyevaporated. The resin was washed with water and dried. On test, the resin showe'd'change in color at C. and completely blackened -at- 0., without fusion. In 20 was diiiicult and the filmwaspoor. In20parts '20 parts of benzol, solubility of solvent made from oxidized kerosene, there.

was slow solution. The film was brown. slight y tacky. and very tough.

th'l'he advantages of my invention result from ins produced. The polyhydric alcohols may be used with any of my products from the partial oxidation of mineral oil fractions and the proddrocarbons give especially good'resins in comand may also be directly polymerized with or without the use of a catalyst.

heating. By the terms polymerizing or condensing as used'herein, I mean theaggregating or clotting is more like 'azresinous solid. I claim: I I

In the treatment of a mixture of difi'erent terpene hydrocarbons, the steps consisting of heating said mixture and treating it-with a gas mainly of a plurality of oxygen derivatives of terpene hydrocarbons. and

,resinifying said product.

JHIDYJAm 5o cheapness and excellent qualities of the res- 4 ucts from the partial oxidation of terpene'hytogether of molecules, producing a material which containing free oxygen under conditions produc- .ing a liquid formed 

